JP5113188B2 - Polymeric substrates with fluoroalkoxycarbonyl groups for amine capture - Google Patents

Abstract

Amino-containing materials can be attached to polymeric materials having a pendant amine capture group that includes a fluoroalkoxycarbonyl group. An amino-containing material can react with the pendant amine capture group by a nucleophilic substitution reaction. The product of the reaction is an alcohol and a pendant group that contains a carbonylimino group. The reaction results in the connection of the amino-containing material to the polymeric material. The polymeric materials are often disposed on a surface of a substrate and the connection of the amino-containing material to the polymeric material results in the immobilization of the amino-containing material on the substrate.

Description

(Cross-reference of related applications)
This application claims priority from US Provisional Patent Application No. 60 / 871,294 filed on Dec. 21, 2006 and U.S. Patent Application No. 11 / 856,144 filed on Sep. 17, 2007. And their disclosures are incorporated herein by reference.

(Field of Invention)
A method for bonding an amino-containing material to a polymeric material and a method for immobilizing the amino-containing material on a substrate are described.

  Use amino-containing materials for many applications, such as amino-containing analytes, amino acids, DNA, RNA, proteins, cells, tissues, organelles, immunoglobulins, or fragments thereof immobilized on the surface of a substrate. Can do. For example, immobilized biological amino-containing materials can be used for medical diagnosis of diseases or genetic defects, for biological separation, or for detection of various biomolecules. Immobilization of an amino-containing material is usually performed by a reaction between an amino group and a reactive functional group covalently bonded to the substrate surface.

  A substrate having an amino-reactive functional group can be prepared by coating the substrate with a solution of a polymeric material containing the amino-reactive functional group. Alternatively, a substrate having an amino reactive functional group can be prepared by coating the substrate with a solution of a monomer containing the amino reactive functional group and then polymerizing the monomer. Representative amino-reactive monomers include, for example, N-[(meth) acryloxy] succinimide and vinyl azlactone. Amino-containing materials can react with N-acyloxysuccinimide groups resulting in displacement of N-hydroxysuccinimide and formation of carboxamides. Amino-containing materials can react with cyclic azlactone to provide ring opening of the cyclic structure.

  Although polymeric surfaces that contain reactive functional groups such as N-acyloxysuccinimide groups or azlactone groups can readily react with primary or secondary amino-containing materials, such reactive functional groups are subject to a number of drawbacks. You may be troubled. For example, many reactions with biological amino-containing materials occur in dilute aqueous solutions. Under these conditions, the N-acyloxysuccinimide functional group is known to hydrolyze rapidly. This competitive reaction can cause incomplete or inefficient immobilization of the amino-containing material on the substrate.

  The azlactone functional group is more stable against hydrolysis, but it is difficult to synthesize azlactone bonded to any polymerizable group other than the vinyl group. The resulting polymeric material has an amino-reactive functional group bonded directly to the polymer backbone. In some applications, this can make it difficult for the amino-containing material to get close enough to the amine reactive group for efficient immobilization.

  A method for bonding an amino-containing material to a polymeric material and a method for immobilizing the amino-containing material on a substrate are described. More specifically, the amino-containing material can be attached to a polymeric material that includes a pendant amine capture group. The pendant amine capture group comprises a fluoroalkoxycarbonyl group capable of undergoing a nucleophilic substitution reaction with a primary or secondary amino-containing material. The partially reacted polymeric material is described to include both reacted and unreacted pendant amine capture groups. Articles comprising partially reacted polymeric materials are also described.

  In one aspect, a method for coupling an amino-containing material to a polymeric material is described. The method includes providing a polymeric material comprising a pendant amine capture group of formula I that comprises a fluoroalkoxycarbonyl group.

In formula I, the variable n is equal to 0 or 1. The group Q is either carbonyloxy or carbonylimino. The group Y is a divalent group including alkylene, heteroalkylene, arylene, or combinations thereof, optionally further including carbonyl, carbonyloxy, carbonylimino, oxy, —NR ³ —, or combinations thereof. , A divalent group. The group R ¹ is selected from hydrogen, fluoro, alkyl, or lower fluoroalkyl, each R ² is lower fluoroalkyl, and R ³ is selected from hydrogen, alkyl, aryl, or aralkyl. The asterisk ( ^* ) indicates the binding site of the pendant group to the main chain of the polymer material. The method further includes the step of (1) reacting the primary or secondary amino-containing material with (2) the fluoroalkoxycarbonyl group of the pendant amine capture group resulting in attachment of the amino-containing group to the polymeric material.

  In another aspect, a method for immobilizing an amino-containing material on a substrate is described. The method includes providing a substrate and placing a polymeric material on a surface of the substrate, the polymeric material comprising:

It has a pendant amine capture group of formula I that contains a fluoroalkoxycarbonyl group. The method further includes the step of (1) reacting the primary or secondary amino-containing material with (2) the fluoroalkoxycarbonyl group of the pendant amine capture group resulting in attachment of the amino-containing group to the polymeric material. The variable n and the groups Q, Y, R ¹ and R ² are the same as defined above for formula I.

  In another aspect, a method for immobilizing an amino-containing material on a substrate is described. The method consists of providing a substrate and placing the reaction mixture on the surface of the substrate. The reaction mixture comprises (a) an amine capture monomer of formula II containing a fluoroalkoxycarbonyl group;

(B) a crosslinking monomer containing at least two (meth) acryloyl groups. In formula II, the variable n is equal to 0 or 1. The group Q is either carbonyloxy or carbonylimino. The group Y is a divalent group including alkylene, heteroalkylene, arylene, or combinations thereof, optionally further including carbonyl, carbonyloxy, carbonylimino, oxy, —NR ³ —, or combinations thereof. , A divalent group. The group R ¹ is selected from hydrogen, fluoro, alkyl, or lower fluoroalkyl, each R ² is lower fluoroalkyl, R ³ is selected from hydrogen, alkyl, aryl, or aralkyl, and R ⁴ is , Hydrogen or alkyl. The method further includes curing the reaction mixture to form a crosslinked polymeric material having pendant amine capture groups. The method still further comprises the step of (1) reacting the primary or secondary amino-containing material with (2) the fluoroalkoxycarbonyl group of the pendant amine capture group resulting in attachment of the amino-containing group to the polymeric material. .

  In yet another aspect, a partially reacted polymeric material is described. The polymeric material comprises (a) a first pendant amine capture group of formula I containing a fluoroalkoxycarbonyl group, and (b) a primary or secondary amino-containing material and a second pendant amine capture group of formula I. And a carbonylimino-containing pendant group.

  In yet another aspect, an article is described. The article includes a substrate and a polymeric material disposed on the surface of the substrate. The polymeric material comprises (a) a first pendant amine capture group of formula I containing a fluoroalkoxycarbonyl group, and (b) a primary or secondary amino-containing material and a second pendant amine capture group of formula I. And a carbonylimino-containing pendant group.

  The terms “a”, “an”, and “the” are used interchangeably with “at least one” to mean one or more of the elements being described.

  The term “alkoxy” refers to a monovalent group of formula —OR where R is an alkyl group.

  The term “alkoxycarbonyl” refers to a monovalent group of formula — (CO) OR where R is an alkyl group.

  The term “alkyl” refers to a monovalent group that is a radical of an alkane and includes groups that are linear, branched, cyclic, or combinations thereof. The alkyl group usually has 1 to 30 carbon atoms. In some embodiments, the alkyl group contains 1-20 carbon atoms, 1-10 carbon atoms, 1-6 carbon atoms, or 1-4 carbon atoms. Examples of alkyl groups include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, n-hexyl, cyclohexyl, n-heptyl, n-octyl, and ethylhexyl. However, it is not limited to these.

  The term “alkylene” refers to a divalent group that is a radical of an alkane. The alkylene can be linear, branched, cyclic, or combinations thereof. Typically the alkylene has 1 to 200 carbon atoms. In some embodiments, the alkylene is 1-100 carbon atoms, 1-80 carbon atoms, 1-50 carbon atoms, 1-30 carbon atoms, 1-20 carbon atoms, Contains 1 to 10 carbon atoms, or 1 to 4 carbon atoms. The radical center of the alkylene can be on the same carbon atom (ie, alkylidene) or on different carbon atoms.

  The term “aralkyl” refers to a monovalent group that is a radical of the compound R—Ar, where Ar is an aromatic carbocyclic group and R is an alkyl group.

  The term “aryl” refers to a monovalent group that is a radical of an aromatic carbocyclic compound. The aryl can have one aromatic ring or can contain up to 5 other carbocycles that are bonded or fused to the aromatic ring. Other carbocycles can be aromatic, non-aromatic, or combinations thereof. Examples of aryl groups include, but are not limited to, phenyl, biphenyl, terphenyl, anthryl, naphthyl, acenaphthyl, anthraquinonyl, phenanthryl, anthracenyl, pyrenyl, perylenyl, and fluorenyl.

  The term “arylene” refers to a divalent group that is a radical of an aromatic carbocyclic compound. Arylene can have one aromatic ring or can contain up to five other carbocycles that are bonded or fused to the aromatic ring. Other carbocycles can be aromatic, non-aromatic, or combinations thereof. Exemplary arylene groups have one, two, or three aromatic rings. For example, the arylene group can be phenylene.

  The term “carbonyl” refers to a divalent group of formula — (CO) —.

The term “carbonylimino” refers to a divalent group of formula — (CO) NR ^a —, where R ^a is hydrogen, alkyl, aryl, or aralkyl.

  The term “carbonyloxy” refers to a divalent group of formula — (CO) O—.

  The term “carboxy” refers to a monovalent group of formula — (CO) OH.

The term “fluoroalkyl” means an alkyl having at least one hydrogen atom replaced by a fluorine atom. As used herein, the term “lower fluoroalkyl” refers to a fluoroalkyl having 1, 2, 3, or 4 carbon atoms. Some exemplary fluoroalkyl has one carbon atom, such as -CHF _2, or -CF _3.

The term “fluoroalkoxy” refers to a monovalent group of formula —OR ^f where R ^f refers to fluoroalkyl.

The term “fluoroalkoxycarbonyl” means a monovalent group of formula — (CO) OR ^f , where (CO) means a carbonyl group and R ^f means a fluoroalkyl group. Fluoroalkoxycarbonyl is typically of the formula — (CO) OCR ¹ (R ² ) ₂ , where R ¹ and R ² are defined herein.

The term “heteroalkylene” means a divalent group that is an alkylene having one or more carbon atoms substituted with sulfur, oxygen, or —NR ^b —, where R ^b is hydrogen or alkyl. It is. The heteroalkylene can be linear, branched, cyclic, or combinations thereof and can contain up to 400 carbon atoms and up to 30 heteroatoms. In some embodiments, the heteroalkylene has up to 300 carbon atoms, up to 200 carbon atoms, up to 100 carbon atoms, up to 50 carbon atoms, up to 30 carbon atoms, up to 20 carbon atoms. Contains carbon atoms or up to 10 carbon atoms.

  The term “(meth) acrylate” means a monomer that is acrylate or methacrylate. Similarly, the term “(meth) acrylamide” means a monomer that is acrylamide or methacrylamide.

The term “(meth) acryloyl” refers to an ethylenically unsaturated group of formula CH ₂ ═CR ⁴ — (CO) —, wherein R ⁴ is hydrogen or methyl. A (meth) acryloyl group is usually adjacent to an oxy or —NR ^c — group, where R ^c is hydrogen, alkyl, aryl, or aralkyl.

  The term “oxy” refers to a divalent group of formula —O—.

  The term “thio” refers to a divalent group of formula —S—.

  The term “amine capture monomer” means a monomer having an amine capture group. The term “amine capture group” means a group on a monomer or polymer that can react with an amino-containing material. Amine capture groups often include a fluoroalkoxycarbonyl group.

  The term “amino-containing material” means a material having a primary amino group or a secondary amino group. The amino-containing material can be a biomaterial or a non-biomaterial. Amino-containing materials often have an alkylene group bonded to a primary amino group or a secondary amino group.

  The term “pendant” refers to a group that is attached to the main chain of the polymeric material but is not part of the main chain of the polymeric material. The pendant group does not participate in the polymerization reaction.

  The terms “polymer” and “polymeric material” are used interchangeably and refer to materials prepared from one monomer, such as homopolymers or materials prepared from two or more monomers, such as copolymers, terpolymers, etc. Mean both. Similarly, the term “polymerize” means a process for making a polymeric material that can be a homopolymer, copolymer, terpolymer, and the like.

  The term “room temperature” means a temperature of about 20 ° C. to about 25 ° C. or about 22 ° C. to about 25 ° C.

  The term “substrate” means a solid support. The substrate can have any useful form, including thin films, sheets, membranes, filters, nonwoven or woven fibers, hollow or solid beads, bottles, plates, tubes, rods, pipes, or wafers. However, it is not limited to these. The substrate can be porous or non-porous, rigid or flexible, transparent or opaque, colorless or colored, and reflective or non-reflective. Suitable substrate materials include, for example, polymeric materials, glass, ceramics, metals, metal oxides, hydrated metal oxides, or combinations thereof.

  The above summary is not intended to describe each disclosed embodiment or every implementation of the present invention. The following description will more specifically exemplify representative embodiments. In several places throughout the document, guidance is provided through lists of examples, which examples can be used in various combinations. In each case, the listed list is given only as a representative group and should not be interpreted as an exclusive list.

  The amino-containing material can be bound to a polymeric material having a pendant amine capture group. More specifically, the pendant amine capture group comprises a fluoroalkoxycarbonyl group that can react with a primary or secondary amino-containing material by a nucleophilic substitution reaction. The product of the reaction is an alcohol and a pendant group containing a carbonylimino group. The reaction results in the binding of the amino-containing material to the polymeric material. The polymeric material is often placed on the surface of the substrate, and binding of the amino-containing material to the polymeric material results in immobilization of the amino-containing material on the substrate.

  In one aspect, a method for coupling an amino-containing material to a polymeric material is described. The method includes providing a polymeric material comprising a pendant amine capture group of formula I that comprises a fluoroalkoxycarbonyl group.

In formula I, the variable n is equal to 0 or 1. The group Q is carbonyloxy or carbonylimino. The group Y is a divalent group including alkylene, heteroalkylene, arylene, or combinations thereof, optionally further including carbonyl, carbonyloxy, carbonylimino, oxy, —NR ³ —, or combinations thereof. , A divalent group. The group R ¹ is selected from hydrogen, fluoro, alkyl, or lower fluoroalkyl, R ² is lower fluoroalkyl, and R ³ is selected from hydrogen, alkyl, aryl, or aralkyl. The asterisk ( ^* ) means the binding site of the pendant group to the main chain of the polymer material. The method further includes reacting the primary or secondary amino-containing material with the fluoroalkoxycarbonyl group of the pendant amine capture group resulting in attachment of the amino-containing group to the polymeric material. The reaction results in nucleophilic substitution of the alcohol of formula HO—CR ¹ (R ² ) ₂ and formation of a pendant group containing a carbonylimino group.

  The pendant amine capture group of the polymeric material is usually attached to the main chain of the hydrocarbon polymer. The polymeric material is typically a reaction product of free radical polymerization of a reaction mixture containing an amine capture monomer. The amine capture monomer has both an ethylenically unsaturated group and an amine capture group. These amine capture monomers are usually of formula II.

In Formula II, the variables n, Q, Y, R ¹ , and R ² are the same as defined for Formula I. The group R ⁴ is selected from hydrogen or alkyl. In many embodiments, R ⁴ is hydrogen or methyl.

  When the variable n is equal to 0, the amine capture monomer of formula II is formula IIa

  The resulting polymeric material contains a pendant amine capture group of formula Ia.

  When the variable n is equal to 1, the amine capture monomer of formula II is formula IIb

  The resulting polymeric material contains a pendant amine capture group of formula Ib.

  The polymeric material having a pendant group of formula Ib has a spacer group (ie, -QY-) between the backbone of the polymeric material and the amine capture group (ie, fluoroalkoxycarbonyl group).

Both the pendant amine capture group of formula I and the amine capture monomer of formula II contain a fluoroalkoxycarbonyl group of formula — (CO) OCR ¹ (R ² ) ₂ , where R ¹ is hydrogen, fluoro, alkyl , Or lower fluoroalkyl, and each R ² is selected from lower fluoroalkyl. Suitable alkyl groups for R ¹ usually have 1 to 10, 1 to 6, or 1 to 4 carbon atoms. Suitable lower fluoroalkyl groups for R ¹ and R ² usually have 1 to 4 carbon atoms. Some exemplary lower fluoroalkyl groups have one carbon atom, such as —CHF ₂ or —CF ₃ .

In some monomers or pendant groups, the fluoroalkoxycarbonyl group is selected from — (CO) OCH (CF ₃ ) ₂ , where R ¹ is hydrogen and each R ² is —CF ₃ or _{- (CO) OC (CF 3} ) _3, and wherein, ^{R 1} and each ^{R 2} is -CF _3. In other exemplary monomers and pendant groups, the fluoroalkoxycarbonyl group is selected from — (CO) OCF (CF ₃ ) ₂ , where R ¹ is fluoro and R ² is —CF ₃ is there.

The group Q is either a carbonyloxy group of formula-(CO) O- or a carbonylimino group of formula-(CO) -NR ^3- , wherein R ³ is hydrogen, alkyl, aryl, or aralkyl. Selected from. Suitable alkyl groups for R ³ often have 1 to 10, 1 to 6, or 1 to 4 carbon atoms. An exemplary aryl R ³ group is phenyl. Exemplary aralkyl R ³ groups are alkyl having 1-10 carbon atoms substituted with phenyl, alkyl having 1-6 carbon atoms substituted with phenyl, or 1-4 substituted with phenyl. Examples include, but are not limited to, alkyl having 1 carbon atom.

Y is a divalent group including alkylene, heteroalkylene, arylene, or a combination thereof. The group Y can optionally further comprise carbonyl, carbonyloxy, carbonylimino, oxy, thio, —NR ³ —, or combinations thereof. The group R ³ is selected from hydrogen, alkyl, aryl, or aralkyl. The group Y usually does not contain a peroxy (ie —O—O—) linkage.

In some embodiments, the group Y can be alkylene, or the group Y can be a first alkylene and a heteroalkylene, arylene, second alkylene, carbonyl, carbonyloxy, attached thereto. It can include at least one other group selected from oxy, thio, —NR ³ —, or combinations thereof. In other embodiments, the group Y can be heteroalkylene or the group Y can be a first heteroalkylene and an arylene, alkylene, second heteroalkylene, carbonyl, carbonyloxy bonded thereto. , Oxy, thio, —NR ³ —, or a combination thereof can include at least one other group. In still other embodiments, the group Y can be arylene or the group Y can be the first arylene and the alkylene, heteroalkylene, second arylene, carbonyl, carbonyloxy, attached thereto. It can include at least one other group selected from oxy, thio, —NR ³ —, or combinations thereof.

  Some exemplary pendant amine capture groups have an alkylene group Y, as shown in Formula Ic.

  In the formula Ic, the variable p is an integer of 1-20. Representative compounds include those where p is an integer of 15 or less, 10 or less, 8 or less, 6 or less, 4 or less, 3 or less, or 2 or less. Such pendant groups can be provided, for example, from free radical polymerization of reaction mixtures containing amine capture monomers of formula IIc.

The groups R ¹ , R ² , and R ⁴ are the same as those previously described for formulas I and II.

  Other exemplary pendant amine capture groups can have a heteroalkylene group Y, as shown in Formula Id or Ie.

  In formula Id or Ie, each variable p is independently an integer from 1 to 20, and D is oxy, thio, or —NH—. Representative compounds include those where p is an integer of 15 or less, 10 or less, 8 or less, 6 or less, 4 or less, 3 or less, or 2 or less. Such pendant groups can be provided, for example, from free radical polymerization of reaction mixtures containing amine capture monomers of formula IId or IIe.

The groups R ¹ , R ² , and R ⁴ are the same as those previously described for formulas I and II.

In other exemplary pendant amine capture groups of Formula I, Y is a second alkylene or first hetero, depending on a group selected from carbonyl, carbonyloxy, carbonylimino, oxy, thio, or —NR ³ —. Includes a first alkylene linked to an alkylene group. The additional alkylene or heteroalkylene group may be linked to the second alkylene or first heteroalkylene group by a group selected from carbonyl, carbonyloxy, carbonylimino, oxy, thio, or —NR ³ —. it can. In yet other exemplary pendant amine capture groups of formula I, Y is a second heteroalkylene or first group, depending on a group selected from carbonyl, carbonyloxy, carbonylimino, oxy, thio, or —NR ³ —. Including a first heteroalkylene linked to the alkylene group. The additional alkylene or heteroalkylene group may be linked to the second alkylene or first heteroalkylene group by a group selected from carbonyl, carbonyloxy, carbonylimino, oxy, thio, or —NR ³ —. it can.

  For example, the pendant amine capture group can be of formula If, Ig, or Ih.

  In formulas If, Ig, and Ih, each D is independently oxy, thio, or —NH—, m is an integer from 1 to 15, k is an integer from 2 to 4, p is an integer of 1-20. In typical compounds, p is an integer of 15 or less, 10 or less, 8 or less, 6 or less, 4 or less, 3 or less, or 2 or less, and m is 10 or less, 5 or less, 2 or less, 1 or less. Things. Such pendant amine capture groups can be provided, for example, from free radical polymerization of reaction mixtures containing amine capture monomers of formula IIf, IIg, or IIh.

The groups R ¹ , R ² , and R ⁴ are the same as those previously described for formulas I and II. For many such pendant amine capture groups, k is equal to 2, D is oxy, m is equal to 1, and p is 3 or less.

  Several factors can influence the choice of group Y for a particular application. These factors include, for example, the ease of amine capture monomer synthesis, the compatibility or reactivity of the amine capture monomer with the crosslinking monomer, if any, and the reactivity or selectivity of the amine capture group with the amino-containing material. Can be mentioned. For example, the size and polarity of the group Y can affect the reactivity of the amine capture group with the amino-containing material. That is, the reactivity of the amine capture group can be altered by changing the length of group Y, the composition of group Y, or both. Similarly, the size and nature of amine capture groups can affect surface concentration and reactivity with amino-containing materials. If desired, various groups in the amine capture monomer can be selected to provide monomers that are liquid at ambient temperature. Liquid monomers are useful in solventless coating compositions that may rather be environmentally desirable.

  Representative pendant amine capture groups include, but are not limited to:

  These polymers with pendant amine capture groups can each be prepared from free radical polymerization of reaction mixtures containing the following amine capture monomers.

Any method known in the art can be used to prepare the monomer of formula II. For example, some monomers can be prepared by reacting a cyclic anhydride with a hydroxy-substituted (meth) acrylate ester. This reaction results in the formation of a (meth) acrylate ester having a carboxy group. The carboxy group can be reacted with thionyl chloride to form a (meth) acrylate ester having a halocarbonyl group. The halocarbonyl group can then be reacted with an alcohol of formula HOCR ₁ (R ₂ ) ₂ in the presence of an acid acceptor, where R ¹ and R ² are defined above. Alternatively, the halocarbonyl group can be reacted with (R ² ) ₂ CFO ⁻ K ⁺ , which is an adduct of KF and perfluoroketone formed in situ. Similar transformations have been reported in the literature for acryloyl chloride to produce compounds of formula II, where n is equal to 0.

  The polymeric material containing the pendant amine capture group of Formula I can be a linear, soluble polymer, or an insoluble, crosslinked polymer. When referring to a polymeric material, the term “soluble” means that the polymeric material is soluble in an amount of at least 0.01% by weight in water or at least one organic solvent at room temperature. Similarly, when referring to a polymeric material, the term “insoluble” means that the polymeric material is not soluble in water or at least one organic solvent in an amount of at least 0.01% by weight at room temperature. To do. Typical organic solvents include alcohols (eg, methanol, ethanol, 1-propanol, 2-propanol, 2-methyl-2-propanol, 1-butanol, and 2-butanol), nitriles (eg, acetonitrile), alkanes. (Eg, cyclohexane or hexane), ethers (eg, fluorinated ethers such as tetrahydrofuran and hydrofluoroethers and hydrochlorofluoroethers), ketones (eg, acetone, methyl ethyl ketone, methyl isobutyl ketone, or N-methylpyrrolidone), aromatic A compound (eg, benzene, toluene, or xylene), an ester (eg, ethyl acetate), a chlorinated hydrocarbon (eg, a chlorine-substituted alkane), a fluorinated hydrocarbon (eg, a fluorine-substituted alkane), or These combinations include, but are not limited to.

  Linear, soluble polymeric materials are usually synthesized in the absence of a crosslinker. That is, to prepare a linear, soluble polymeric material, reaction mixtures containing amine capture monomers usually do not contain a crosslinker. Reaction mixtures used to prepare such polymeric materials often contain from 0.1 to 100% by weight of the amine capture monomer of formula II, based on the weight of monomers in the monomer mixture. To do.

  In contrast, insoluble, crosslinked polymeric materials are usually polymerized in the presence of a crosslinking agent. That is, to prepare an insoluble, crosslinked polymeric material, the reaction mixture containing the amine capture monomer also typically contains a crosslinking agent having at least two (meth) acryloyl groups. When preparing a cross-linked polymeric material, the reaction mixture is often 0.1-90 wt% amine capture monomer of Formula II and 10-99.9 wt%, based on the weight of monomers in the monomer mixture. Containing a cross-linking monomer.

  Suitable crosslinking monomers for the preparation of insoluble, crosslinked polymeric materials include di (meth) acrylate, tri (meth) acrylate, tetra (meth) acrylate, penta (meth) acrylate and the like. These (meth) acrylates are, for example, alkanediols (ie, alkane substituted with two hydroxy groups), alkanetriols (ie, alkane substituted with three hydroxy groups), alkanetetraols (ie, four hydroxy groups). Can be formed by reacting (meth) acrylic acid with alkanepentaol (ie, alkane substitution with five hydroxy groups).

  Typical crosslinking monomers include 1,2-ethanediol di (meth) acrylate, 1,12-dodecanediol di (meth) acrylate, 1,4-butanediol di (meth) acrylate, and 1,6-hexanediol. Di (meth) acrylate, trimethylolpropane triacrylate (eg, from Surface Specialties (Smyrna, Ga.) Under the trade name TMPTA-N) and Sartomer under the trade name SR-351. ) (Commercially available from Exton, Pa.), Pentaerythritol triacrylate (eg, commercially available from Sartomer under the trade name SR-444), tris (2-hydroxyethyl isocyanurate) Triacrylate (SR-368 ), A mixture of pentaerythritol triacrylate and pentaerythritol tetraacrylate (e.g., PETIA (tetraacrylate to triacrylate about 1: 1 from Surface Specialties)). ) And PETA-K (commercially available under the trade name of tetraacrylate to triacrylate in a ratio of about 3: 1), pentaerythritol tetraacrylate (e.g., sultomer under the trade name SR-295) (Commercially available from Sartomer), ditrimethylolpropane tetraacrylate (eg, commercially available from Sartomer under the trade name SR-355), ethoxylated pentaerythritol tetraacrylate (eg, SR-49). 4) and dipentaerythritol pentaacrylate (for example, commercially available from Sartomer under the trade name SR-399). Mixtures of crosslinking monomers can be used.

  Other monomers, such as optional diluent monomers, can be included in the reaction mixture used to prepare either a linear, soluble polymeric material, or a crosslinked, insoluble polymeric material. Suitable diluent monomers are usually (meth) acrylates or (meth) acrylamides that contain only one (meth) acryloyl group and no amine capture group.

  Some representative (meth) acrylate diluent monomers are methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (Meth) acrylate, tertiary butyl methacrylate, n-hexyl (meth) acrylate, cyclohexyl (meth) acrylate, 3,3,5-trimethylcyclohexyl (meth) acrylate, 2-methylbutyl (meth) acrylate, 2-ethylhexyl ( (Meth) acrylate, 4-methyl-2-pentyl (meth) acrylate, n-octyl (meth) acrylate, isooctyl (meth) acrylate, n-decyl (meth) acrylate, isodecyl (meth) acrylate, lauryl (meth) Acrylate, alkyl (meth) acrylates such as isononyl (meth) acrylate, isotridecyl (meth) acrylate, and behenyl (meth) acrylate.

  Other exemplary (meth) acrylate diluent monomers are aryl (meth) acrylates such as phenyl (meth) acrylate, stearyl (meth) acrylate, and benzyl (meth) acrylate. Still other representative (meth) acrylate diluent monomers are hydroxy, such as 2-hydroxyethyl (meth) acrylate and 3-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, glycerol (meth) acrylate, and the like. Alkyl (meth) acrylate. Additional exemplary (meth) acrylate diluent monomers are ether-containing (meth) acrylates such as 2-ethoxyethyl (meth) acrylate, 2-methoxyethyl (meth) acrylate, polyethylene glycol (meth) acrylate, and the like. The diluent monomer is a nitrogen-containing (meth) acrylate such as N, N-dimethylaminoethyl (meth) acrylate, N, N-dimethylaminopropyl (meth) acrylate, or 2-trimethylammoniumethyl (meth) acrylate halogen compound. be able to. The diluent monomer can also be (meth) acrylamide, N, N-dialkyl (meth) acrylamide, and the like.

  Some reaction mixtures contain a solvent. Suitable organic solvents include water, alcohols (eg, methanol, ethanol, 1-propanol, 2-propanol, 2-methyl-2-propanol, 1-butanol, and 2-butanol), nitriles (eg, acetonitrile), Alkanes (eg cyclohexane or hexane), ethers (eg fluorinated ethers such as tetrahydrofuran and hydrofluoroethers and hydrochlorofluoroethers), ketones (eg acetone, methyl ethyl ketone, methyl isobutyl ketone or N-methylpyrrolidone), aromatic Group compounds (eg, benzene, toluene, or xylene), esters (eg, ethyl acetate), chlorinated hydrocarbons (eg, chlorine-substituted alkanes), fluorinated hydrocarbons (eg, fluorine-substituted alkanes), Although combinations thereof, without limitation. Other reaction mixtures can be solvent-free. Exemplary solventless reaction mixtures include those where the amine capture monomer is a liquid or those where the reaction mixture is a coated composition with the solvent removed.

  The reaction mixture is usually polymerized using a free radical polymerization method. In many cases, there is an initiator present in the reaction mixture. The initiator can be a thermal initiator, a photoinitiator, or both. The initiator is often 0.1 to 5%, 0.1 to 3%, 0.1 to 2%, or 0.1 to 0.1% by weight, based on the weight of monomers in the reaction mixture. Used at a concentration of 1% by weight.

  When a thermal initiator is added to the reaction mixture, the crosslinked polymer can be formed at room temperature (ie, 20-25 ° C.) or at an elevated temperature. The temperature required for the polymerization often depends on the particular thermal initiator used. Examples of the thermal reaction initiator include organic peroxides or azo compounds. Azo compounds are commercially available, for example, from DuPont, Wilmington, Del., Under the trade name VAZO, such as VAZO 67.

  When a photoinitiator is added to the reaction mixture, a crosslinkable polymeric material can be formed by applying actinic radiation until the composition gels or hardens. Suitable actinic radiation includes electromagnetic radiation in the infrared region, visible region, ultraviolet region, or combinations thereof.

  Examples of suitable photoinitiators in the ultraviolet region include benzoin, benzoin alkyl ethers (eg, benzoin methyl ether and substituted benzoin alkyl ethers such as anisoin methyl ether), phenones (eg, 2,2-dimethoxy- Substituted acetophenones such as 2-phenylacetophenone and substituted α-ketols such as 2-methyl 2-hydroxypropiophenone), phosphine oxides, polymer photoinitiators, and the like, but are not limited thereto.

  Commercially available photoinitiators include 2-hydroxy-2-methyl-1-phenyl-propan-1-one (eg, commercially available from Ciba Specialty Chemicals under the trade name IRGACURE 1173). A mixture of 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide and 2-hydroxy-2-methyl-1-phenyl-propan-1-one (for example, Ciba Specialty Chemicals). Commercially available under the trade name DAROCUR 4265), 2,2-dimethoxy-1,2-diphenylethane-1-one (eg, Ciba Specialty Chemicals, IRGACURE). ) (Commercially available under the trade name 651), bis (2,6-dimethoxy) A mixture of benzoyl) -2,4,4-trimethyl-pentylphosphine oxide and 1-hydroxy-cyclohexyl-phenyl-ketone (for example, commercially available from Ciba Specialty Chemicals under the trade name IRGACURE 1800) ), A mixture of bis (2,6-dimethoxybenzoyl) -2,4,4-trimethyl-pentylphosphine oxide (eg, trade name of IRGACURE 1700 from Ciba Specialty Chemicals) 2-methyl-1,1 [4- (methylthio) phenyl] -2-morpholinopropan-1-one (eg, IRGACURE 907 trademark from Ciba Specialty Chemicals) Marketed by name), 1-hydroxy-cyclohexyl-phenyl-ketone (for example, commercially available from Ciba Specialty Chemicals under the trade name IRGACURE 184), 2-benzyl-2- (dimethylamino) -1 -[4- (4-morpholinyl) phenyl] -1-butanone (commercially available from Ciba Specialty Chemicals under the trade name IRGACURE 369), bis (2,4,4 6-trimethylbenzoyl) -phenylphosphine oxide (commercially available from Ciba Specialty Chemicals under the trade name IRGACURE 819), ethyl-2,4,6-trimethylbenzoyldiphenylphosphine (Eg BASF (North Carolina) Commercially available under the trade name LUCIRIN TPO-L) from Charlotte, Ind.), And 2,4,6-trimethylbenzoyldiphenylphosphine oxide (eg BASF (Charlotte, NC)) Such as, but not limited to, the commercial name of LUCIRIN TPO).

  Suitable photoinitiators for use in the visible region often include electron donors and electron acceptors such as iodonium salts and visible light sensitizing compounds such as α-diketones. Such photoinitiators include, for example, US Patent Publication No. 2005/0113477 (Oxman et al.) And US Patent Publication No. 2005/0070627 (Falsafi et al.), And US Pat. 765,036 (Dede et al.).

  The resulting polymeric material, which can be linear and soluble, or cross-linked and insoluble, has a pendant amine capture group containing a fluoroalkoxycarbonyl group. The fluoroalkoxycarbonyl group of the pendant amine capture group can undergo a nucleophilic substitution reaction with a primary amino-containing material or a secondary amino-containing material as shown in Reaction Scheme A below.

The product of the nucleophilic substitution reaction comprises an alcohol of formula HO—CR ¹ (R ² ) ₂ as well as a pendant group of formula III. The pendant group of formula III contains a carbonylimino group of formula-(CO) -NR ^5- . Formation of a carbonylimino-containing pendant group of formula III results in attachment of the amino-containing material to the polymeric material.

In reaction Scheme A, NHR 5 ^-T indicates an expression for the primary amino-containing material or secondary amino-containing material. The group R ⁵ is selected from hydrogen, alkyl, or part of a cyclic structure. The group T is equal to the residue of the amino-containing material in the absence of the amino group (—NHR ⁵ ). The amino group is often attached to an alkylene group in the amino-containing material. Suitable amino-containing materials that can be represented by the chemical formula NHR ⁵ -T include amino-containing analytes, amino acids, DNA, RNA, proteins, cells, tissues, organelles, immunoglobulins, or fragments thereof. It is not limited.

  Where the amino-containing material has a plurality of primary amino groups, secondary amino groups, or combinations thereof, the plurality of amino groups can be reacted with a number of pendant amine capture groups of Formula I. Thus, a polymeric material having multiple amine capture groups can have one or more pendant groups attached to a single amino-containing material. Similarly, polymeric materials having multiple amine capture groups can be reacted with multiple amino-containing materials. These amino-containing materials can have single or multiple amino groups.

  In some embodiments, only a portion of the pendant amine capture group of the polymeric material is reacted with the amino-containing material. That is, there are excess pendant amine capture groups containing fluoroalkoxycarbonyl groups. Excess pendant amine capture groups may be desirable and tend to favor the capture of any amino-containing material that may be present. The partially reacted polymeric material, such as the polymeric material prior to reacting with the amino-containing material, can be linear or cross-linked.

  More specifically, the partially reacted polymeric material comprises: (a) a first pendant amine capture group of formula I that contains a fluoroalkoxycarbonyl group;

  (B) including a mixture of pendant groups, including carbonylimino-containing pendant groups of Formula III.

A carbonylimino-containing pendant group is the reaction product of a second pendant amine capture group of formula I with a primary or secondary amino-containing material. The variable n and the groups Q, Y, R ¹ , R ² , R ⁵ , and T are the same as defined above.

  According to Formula I, pendant fluoroalkoxycarbonyl groups usually have improved hydrolytic stability compared to derivatives of N-hydroxysuccinimide, which is a known group for reacting with amino-containing materials. . Due to the improved hydrolytic stability of the pendant amine capture group of formula I, polymeric materials can usually be used in aqueous systems. The reaction rate of the amino-containing material with the fluoroalkoxycarbonyl group of the pendant amine capture group of formula I is usually faster than the hydrolysis rate of the fluoroalkoxycarbonyl group. That is, the binding of the amino-containing material occurs faster than the hydrolysis reaction. The attached amino-containing material is not easily displaced due to the formation of a covalent carbonylimino bond.

  A polymeric material having a pendant amine capture group of Formula I can be disposed on a substrate. When the polymeric material is disposed on the substrate and the amino-containing material is attached to the polymeric material by reacting with a pendant amine capture group, the amino-containing material is immobilized on the substrate.

  If the polymeric material is a linear, soluble polymer, the polymeric material is often prepared prior to placement on the surface of the substrate. That is, the method for immobilizing an amino-containing material on a substrate includes a step of providing a substrate and a step of disposing a polymer material on the surface of the substrate, wherein the polymer material is a fluoropolymer. It has a pendant amine capture group of formula I that contains an alkoxycarbonyl group.

The variable n and the groups Q, Y, R ¹ and R ² are the same as defined above. The method further includes reacting the amino-containing material with a fluoroalkoxycarbonyl group of a pendant amine capture group that results in attachment of the amino-containing group to the polymeric material.

  When the polymeric material is a cross-linked, insoluble polymer, the polymeric material is typically polymerized while in contact with the substrate. More specifically, a method for immobilizing an amino-containing material on a substrate includes the steps of providing a substrate and placing a reaction mixture on the surface of the substrate. The reaction mixture comprises (a) an amine capture monomer of formula II containing a fluoroalkoxycarbonyl group;

(B) a crosslinking monomer containing at least two (meth) acryloyl groups. In formula II, the variable n and the groups Q, Y, R ¹ , R ² , and R ⁴ are the same as defined above. The method includes curing the reaction mixture to form a crosslinked polymeric material having pendant amine capture groups, reacting a primary or secondary amino-containing material with a fluoroalkoxycarbonyl group of the pendant amine capture group; Is further included. This reaction results in the binding of the amino-containing material to the polymeric material by a nucleophilic substitution reaction.

  The method of immobilization can result in the formation of an article comprising a substrate and a partially reacted polymeric material disposed on the surface of the substrate. The partially reacted polymeric material comprises a mixture of pendant groups comprising (a) a first fluoroalkoxycarbonyl group of formula I and (b) a carbonylimino-containing pendant group of formula III.

  In some embodiments, the reaction mixture wets the surface of the substrate and the resulting cross-linked polymeric material adheres to the surface of the substrate. The crosslinked polymeric material adheres without forming a covalent bond between the reactive group on the polymer and the complementary group on the surface of the substrate. Rather, the polymer adheres by joining with surface defects on the substrate.

  The cross-linked polymeric material can be patterned on the substrate. That is, the reaction mixture can be applied to the surface of the substrate. The pattern can be in the form of text, pattern, image, and the like. For example, the pattern can be in the form of a dot, square, rectangle, circle, line, or wave (eg, square wave, sine wave, or sawtooth wave).

  One method of forming a patterned cross-linked polymeric material is to place a pattern of the reaction mixture on the surface of the substrate by screen printing, jet printing (eg, spray jet, valve jet, or ink jet printing), etc. Is mentioned. Useful devices for jet printing are described, for example, in US Pat. No. 6,513,897 (Tokie) and US Pat. No. 6,883,908 B2 (Young et al.). . After applying the pattern to the surface of the substrate, the reaction mixture can be cured. For example, the reaction mixture may be cured by heating if a thermal initiator is included in the reaction mixture or by applying actinic radiation if a photoinitiator is included in the reaction mixture. Can do.

  As another method for forming a patterned cross-linked polymer material, a step of forming a layer of a reaction mixture on a substrate, a first portion of the reaction mixture is cured, and a cross-linkable polymer is formed on the substrate. A step of forming a pattern of the material, and a step of removing the second portion of the reaction mixture that has not been cured. The layer of reaction mixture on the substrate is prepared using any suitable technique such as, for example, brush coating, spray coating, gravure coating, transfer roll coating, knife coating, curtain coating, wire coating, and doctor blade coating. Is possible.

  One method of polymerizing a portion of the reaction mixture includes using a photoinitiator in the reaction mixture and using a mask. The mask contains an opening pattern and can be placed between the layer of reaction mixture and the source of actinic radiation. Actinic radiation can penetrate the openings in the mask. When exposed to actinic radiation, the first portion of the reaction mixture layer corresponding to the opening of the mask can polymerize and the second portion of the reaction mixture layer blocked from actinic radiation by the mask is It remains uncured or unreacted. That is, the uncured reaction mixture is a monomer composition that does not gel or cure and does not form a cross-linked polymeric material. The uncured reaction mixture can be removed using a solvent suitable for the monomer of formula II, the crosslinking monomer, and any optional diluent monomer. The solvent typically does not dissolve the cured cross-linked polymeric material due to extensive cross-linking. For this reason, the uncured reactive mixture can be removed while the pattern of the cross-linked polymer material remains on the surface of the substrate.

  Suitable solvents for removing the unreacted reaction mixture include water, acetonitrile, tetrahydrofuran, ethyl acetate, toluene, acetone, methyl ethyl ketone, isopropanol, N-methylpyrrolidone, chlorinated and fluorinated hydrocarbons, fluorinated ethers, or These combinations are included, but are not limited to these. Crosslinked polymeric materials are usually insoluble in these solvents.

  Suitable masks for this patterning method include polymeric materials (eg, polyesters such as polyethylene terephthalate or polyethylene naphthalate, polyimide, polycarbonate, or polystyrene), metal foil materials (eg, stainless steel, other steels, aluminum Or copper), paper, woven or non-woven fabric material, or combinations thereof. Polymer masks and openings in these masks are further described in US Pat. No. 6,897,164 B2 (Baude et al.). The opening of the mask can be any suitable dimension.

  The substrate for immobilization of the amino-containing material can have any useful form, such as a film, sheet, membrane, filter, nonwoven or woven fiber, hollow or solid beads, bottle, plate, tube, Examples include, but are not limited to, rods, pipes, or wafers. The substrate can be porous or non-porous, rigid or flexible, transparent or opaque, colorless or colored, and reflective or non-reflective. The substrate can have a flat or relatively flat surface, or can have a texture such as wells, jagged, channels, bumps, and the like. The substrate can have a single layer or multiple layers of material. Suitable substrate materials include, for example, polymeric materials, glass, ceramics, metals, metal oxides, hydrated metal oxides, or combinations thereof.

  Suitable polymeric substrate materials include polyolefins (eg, polyethylene and polypropylene), polystyrene, polyacrylate, polymethacrylate, polyacrylonitrile, polyvinyl acetate, polyvinyl alcohol, polyvinyl chloride, polyoxymethylene, polycarbonate, polyamide, polyimide, Examples include, but are not limited to, polyurethanes, phenolic resins, polyamines, amino epoxy resins, polyesters, silicones, cellulosic polymers, polysaccharides, or combinations thereof.

  Suitable glass and ceramic substrate materials can include, for example, silicon, aluminum, lead, boron, phosphorus, zirconium, magnesium, calcium, arsenic, gallium, titanium, copper, or combinations thereof. Glass typically includes various types of silicate-containing materials.

  In some embodiments, the substrate comprises a diamond-like glass layer, as disclosed in US Pat. No. 6,696,157 B1 (David et al.). Diamond-like glass is an amorphous material containing carbon, silicon, and one or more elements selected from hydrogen, oxygen, fluorine, sulfur, titanium, or copper. Some diamond-like glass materials are formed from tetramethylsilane precursors using a plasma process. It can be further processed in an oxygen plasma to produce a hydrophobic material for controlling the silanol concentration on the surface.

  Suitable metal-containing materials such as metals, metal oxides or hydrated metal oxides for the substrate are, for example, gold, silver, platinum, palladium, aluminum, copper, chromium, iron, cobalt, nickel, zinc, Etc. can be contained. The metal-containing material can be an alloy such as stainless steel or indium tin oxide. In some embodiments, the metal-containing material is the top layer of the multilayer substrate. For example, the substrate can have a second layer that is a polymer and a first layer that contains a metal. In one embodiment, the second layer is a polymer film and the first layer is a gold thin film. In other embodiments, the multilayer substrate comprises a polymeric film coated with a titanium-containing layer and then with a gold-containing layer. In such a structure, the titanium layer can function as a bonding layer or a primer layer for adhering the gold layer to the polymer film. In other embodiments of the multilayer substrate, the silicon support layer is coated with a layer of chromium and then with a layer of gold. The chromium layer can improve the adhesion of the gold layer to the silicon layer.

  Polymeric materials with pendant amine capture groups and immobilized amino-containing materials can be used in a variety of applications. Immobilized biological amino-containing materials can be useful in medical diagnosis of diseases or genetic defects. Immobilized amino-containing materials can also be used for biological separation or to detect the presence of various biomolecules. Furthermore, the immobilized amino-containing material can be used in a bioreactor or as a biocatalyst to prepare other materials. Pendant amine capture groups containing fluoroalkoxycarbonyl groups can be used to detect amino-containing analytes that are not biological materials. The amino-containing analyte can have a primary amine group, a secondary amine group, or a combination thereof.

  In addition, other materials can be bound to the immobilized amino-containing material. This further bonded material can be combined with the amino-containing material before immobilization of the amino-containing material, or can be bonded to the amino-containing material after immobilization of the amino-containing material. For example, the amino-containing material attached to the polymeric material can be a first biomolecule that is further bound to a second biomolecule. The amino-containing material and further conjugated material can be complementary RNA fragments, complementary DNA fragments, antigen-antibody combinations, immunoglobulin-bacteria combinations, and the like.

  Biological amino-containing materials can often remain active after attachment to a polymeric material (ie, the pendant group according to Formula III includes a biologically active amino-containing material). it can). For example, the immobilized antibody can subsequently bind to the antigen, or the immobilized antigen can subsequently bind to the antibody. Similarly, an immobilized amino-containing biomaterial having a moiety capable of binding to bacteria can subsequently bind to bacteria (eg, immobilized immunoglobulin can subsequently be bound to bacteria such as S. aureus). Can be combined).

  These examples are for illustrative purposes only and are not meant to be limiting on the scope of the appended claims. Unless stated otherwise, all parts, percentages, ratios, etc. described in the examples and the following specification are by weight. Solvents and other reagents used were obtained from Sigma-Aldrich Chemical Company (Milwaukee, Wis.) Unless otherwise noted.

Preparative Example 1: Preparation of glutaryl chloride mono-methacryloxyethyl ester 2-hydroxyethyl methacrylate (57.0 grams), glutaric anhydride (50.0 grams) and phenothiazine (0.15 grams) in dry THF. Was cooled in a glass reaction vessel in an ice / water bath. Triethylamine (46.0 grams in 10 milliliters of THF) was added dropwise to the stirred mixture. The mixture was warmed to room temperature and stirred for 2 days. The solution was concentrated using a rotary evaporator and the remaining mixture was dissolved in CH ₂ Cl ₂ (250 ml). This solution was washed twice with 150 ml of 5% HCl solution and twice with 100 ml of water. After washing, the solution was dried over MgSO ₄ and the solvent was removed on a rotary evaporator to give 105.4 grams of glutaric acid mono-methacryloxyethyl ester as a pink liquid. The glutaric acid mono - Samples of methacryloxyethyl ester (50.0 g) was dissolved in _CH 2 Cl ₂ (100 mL). To this was added phenothiazine (0.05 grams) followed by 5-10 milliliters of thionyl chloride (25 milliliters). The reaction flask was significantly cooled as HCl evolved. The reaction mixture was stirred overnight and the solvent was removed on a rotary evaporator to give 52.0 grams of glutaric acid mono-methacryloxyethyl ester as a pink liquid.

Preparation Example 2: glutaryl chloride mono - hexafluoro the methacryloxyethyl ester - iso - Preparation hexafluoro propyl ester - iso - propanol (8.6 _g), CH 2 _Cl 2 (50 mL), and ethyldiisopropylamine (5.4 grams) was slowly added to the stirred mixture of acid chlorides from Preparative Example 1 (10.5 grams) over several minutes. The resulting mixture was stirred for 2 hours and volatiles were removed using a rotary evaporator. This residue was dissolved in methyl tertiary butyl ether and filtered through a microfilter. The solvent was removed using a rotary evaporator to give 9.0 grams of oil. This oil was dissolved in hexane (20 milliliters) and filtered through a microfilter. The solvent was removed using a rotary evaporator to give 8.5 grams of a clear light brown liquid. The identity of the product was confirmed by proton and fluorine NMR.

Preparation Example 3: glutaryl chloride mono - nonafluoro of methacryloxyethyl ester - tert-butyl ester Preparation nonafluoro - tert-butanol (4.7 grams), phenothiazine (0.007 _g), CH 2 _Cl 2 ( 25 ml), and ethyl diisopropylamine (3.0 grams) were slowly added over several minutes to the stirred mixture of acid chlorides (6.0 grams) from Preparative Example 1. The resulting mixture was stirred overnight. An additional 25 milliliters of CH ₂ Cl ₂ was added and the resulting mixture was washed with water (200 milliliters), 3% HCl solution (50 milliliters), and water (50 milliliters). After washing, the mixture was dried with MgSO ₄ . The solvent was removed on a rotary evaporator to give 7.7 grams of a clear light brown liquid. The identity of the product was confirmed by proton and fluorine NMR.

Preparative Example 4: Preparation of heptafluoro-iso-propyl acrylate. G. It was essentially the same as that described by Pittman et al. In J Polymer Science A-1, 4, 2637 (1966).

A mixture of dry KF (19.2 grams) and dry diglyme (250 milliliters) was added to a reaction vessel equipped with a paddle stirrer, gas inlet, and dry ice condenser. The mixture was cooled to −20 ° C. using a cooling bath, and hexafluoroacetone was added as a gas. The cooling bath was removed and the mixture was warmed to 20 ° C. over 2 hours, after which 26 milliliters of acryloyl chloride was added over 10 minutes. The resulting mixture was stirred for 3 hours. Water was added and the resulting lower organic layer was washed again with water and dried over MgSO ₄ . This organic layer (57.7 grams) was distilled to 22.9 grams of material having a boiling point of 84 ° C.

Preparative Example 5: Preparation of heptafluoro-iso-propyl ester of glutaryl chloride mono-methacryloxyethyl ester A mixture of dry KF (6.3 grams) and dry diglyme (100 milliliters) is -20 <0> C in a cooling bath. And hexafluoroacetone (16.0 grams) was added as a gas. The cooling bath was removed. When the temperature reached 5 ° C. (about 1 hour), the acid chloride from Preparative Example 1 (20.0 grams) was added slowly over 10 minutes. The resulting mixture was stirred at room temperature for 3 hours and quenched with water. The resulting lower organic layer was dissolved in CH ₂ Cl ₂ (25 ml), washed with water and dried over MgSO ₄ . GLC of the resulting solution showed the desired ester as the main constituent.

Example 1
A 10 wt% fluorocarbon solution was prepared by mixing 1.00 grams of the ester prepared in Preparative Example 2, 9.00 grams of TMPTA, and 40.0 grams of ethyl acetate. A 5 wt% fluorocarbon solution was prepared by mixing 4.0 grams of TMPTA and 16.0 grams of ethyl acetate with 20.0 grams of a 10 wt% solution. A 2.5 wt% fluorocarbon solution was prepared by mixing 4.0 grams of TMPTA and 16.0 grams of ethyl acetate with 20.0 grams of a 5 wt% solution. Two drops of photoinitiator were added to each of these solutions (10%, 5% and 2.5%). The resulting solution was coated onto PET film using a # 28 Mayer rod, allowed to air dry for 30 minutes, and UV processor (Fusion UV Systems, Gaithers, MD). (Gaithersburg), model MC-6RQN, H-bulb) to obtain a cured film.

(Example 2)
A 10 wt% fluorocarbon solution was prepared by mixing 1.00 grams of the ester prepared in Preparative Example 3, 9.00 grams of TMPTA, and 40.0 grams of ethyl acetate. A 5 wt% fluorocarbon solution was prepared by mixing 4.0 grams of TMPTA and 16.0 grams of ethyl acetate with 20.0 grams of a 10 wt% solution. A 2.5 wt% fluorocarbon solution was prepared by mixing 4.0 grams of TMPTA and 16.0 grams of ethyl acetate with 20.0 grams of a 5 wt% solution. Two drops of photoinitiator were added to each of these solutions (10%, 5% and 2.5%). The resulting solution was coated onto PET film using a # 28 Mayer rod, allowed to air dry for 30 minutes, and UV processor (Fusion UV Systems, Gaithers, MD). (Gaithersburg), model MC-6RQN, H-bulb) to obtain a cured film.

(Example 3)
A 10 wt% fluorocarbon solution was prepared by mixing 1.00 grams of the ester prepared in Preparative Example 4, 9.00 grams of TMPTA, and 40.0 grams of ethyl acetate. A 5 wt% fluorocarbon solution was prepared by mixing 4.0 grams of TMPTA and 16.0 grams of ethyl acetate with 20.0 grams of a 10 wt% solution. A 2.5 wt% fluorocarbon solution was prepared by mixing 4.0 grams of TMPTA and 16.0 grams of ethyl acetate with 20.0 grams of a 5 wt% solution. Two drops of photoinitiator were added to each of these solutions (10%, 5% and 2.5%). The resulting solution was coated onto PET film using a # 28 Mayer rod, allowed to air dry for 30 minutes, and UV processor (Fusion UV Systems, Gaithers, MD). (Gaithersburg), model MC-6RQN, H-bulb) to obtain a cured film.

Example 4: Heptafluoroisopropyl acrylate homopolymer 113.4 g (4 ounces) of polymerization bottle, 5.0 grams of the ester of Preparation Example 4, 20 grams of HFE 7200, 50 milligrams of thermal reaction Filled with initiator. The solution was purged with 1 liter per minute N ₂ for 1 minute and the sealed bottle was heated in a rotating water bath at 60 ° C. for 24 hours. The obtained polymer was a weak adhesive resin.

Example 5: Copolymer of heptafluoroisopropyl acrylate and butyl methacrylate A 113.4 g (4 ounce) bottle was charged with 5.0 grams of the ester of Preparation Example 4 and 5.0 grams of butyl methacrylate. Charged with 30.0 grams of ethyl acetate and 104 milligrams of thermal initiator. The contents were purged with 1 liter per minute N ₂ and heated in a rotating water bath at 60 ° C. for 24 hours. This copolymer was a clear and colorless resin without stickiness.

Example 6: Copolymer of Preparative Example 2 and Butyl Methacrylate 113.4 g (4 oz) bottle, 3.0 grams of Preparative Example 2 ester, 7.0 grams of butyl methacrylate, 30 Charged with grams of ethyl acetate, 102 milligrams of thermal initiator. The contents were purged with 1 liter per minute N ₂ for 1 minute and heated in a rotating water bath at 60 ° C. for 24 hours. This copolymer was a clear and colorless resin without stickiness.

Claims (3)

A method of bonding an amino-containing material to a polymeric material,
Providing a polymeric material comprising a pendant amine capture group of formula I comprising:

Where
n is equal to 0 or 1,
Q is carbonyloxy or carbonylimino;
Y is a divalent group comprising alkylene, heteroalkylene, arylene, or combinations thereof, optionally further comprising carbonyl, carbonyloxy, carbonylimino, oxy, —NR ³ —, or combinations thereof; A divalent group,
R ¹ is hydrogen, fluoro, alkyl, or lower fluoroalkyl,
R ² is lower fluoroalkyl,
R ³ is hydrogen, alkyl, aryl, or aralkyl,
An asterisk ( ^* ) indicates the binding site of the pendant group to the main chain of the polymeric material;
(1) a primary or secondary amino-containing material, and (2) reacting the fluoroalkoxycarbonyl group of the pendant amine capture group to effect attachment of the amino-containing group to the polymeric material. . The polymeric material is a reaction product of a reaction mixture comprising an amine capture monomer of formula II;

Where
The method of claim 1, wherein R ⁴ is hydrogen or alkyl.   The method of claim 1, wherein the polymeric material is crosslinked.